CN1790171B - Imaging member - Google Patents

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Publication number
CN1790171B
CN1790171B CN200510131472.1A CN200510131472A CN1790171B CN 1790171 B CN1790171 B CN 1790171B CN 200510131472 A CN200510131472 A CN 200510131472A CN 1790171 B CN1790171 B CN 1790171B
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charge generating
photoconductive
generating layer
particle
layer
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CN1790171A (en
Inventor
L·张
C·C·陈
N·L·贝尔克纳普
F·J·罗佩斯
L·-B·林
A·伊安尼迪斯
E·J·小拉迪甘
J·S·钱伯斯
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Xerox Corp
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Xerox Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/095—Oxygen containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0503—Inert supplements
    • G03G5/051—Organic non-macromolecular compounds
    • G03G5/0514—Organic non-macromolecular compounds not comprising cyclic groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0525—Coating methods
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0539—Halogenated polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0542—Polyvinylalcohol, polyallylalcohol; Derivatives thereof, e.g. polyvinylesters, polyvinylethers, polyvinylamines
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0546—Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0696—Phthalocyanines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A process for preparing a charge generating layer comprising dispersing photoconductive phthalocyanine particles in a polymer matrix, the matrix comprising a polymeric film-forming reaction product of vinyl chloride, vinyl acetate, maleic acid, and hydroxyalkyl acrylate, in a solution of n-butyl acetate and methyl isobutyl ketone. An electrophotographic imaging member is also prepared comprising a charge generating layer prepared according to this process.

Description

Image-forming component
Technical field
With multiple embodiments electrophotographic imaging member is described at this, and is described more specifically by in the dicyandiamide solution that uses n-butyl acetate and methyl isobutyl ketone, in polymeric matrix, forming the method that the dispersion of giving birth to electric material prepares image-forming component.
Background technology
In electrofax is used as xerox, make in charge holding surface (being photoconductor, photoreceptor or imaging surface) static electrification lotus and the light pattern that is exposed to the original image that will duplicate and optionally make surface-discharge to take this as a foundation.The charging that obtains on this surface and the pattern of region of discharge form the static charge pattern (electrostatic latent image) that meets original image.By with it be called " toner " but the powder of high degree of dispersion electrostatic attraction contact the development latent image.On image-region, keep toner by lip-deep static charge.Therefore, the bright image with the former figure that duplicates as one man produces toner image.Then toner image is transferred to substrate (as paper) and this image is fixed to the upper to form the permanent recording of the image that will duplicate.After developing, remove the excessive toner that stays at charge holding surface from the surface.
Above-mentioned technology is known and is used for duplicating and using from the printing of the former figure of electron production or storage from the optical lens of former figure, wherein can adopt variety of way to be discharged with image mode in charged surface.Wherein on electric charge maintenance substrate, operate with the ion projection unit affinity ground of image mode deposited charge.
The form of electrophotographic imaging member can be plate, rotary drum or flexible band.These electrofax assemblies normally comprise substrate, conductive layer, non-essential hole blocking layer, non-essential bonding coat, charge generating layer and transmission of electricity layer, non-essential protective seam and the multi-layer photoreceptor of anti-curl back layer in some band embodiments.
The routine techniques that applies cylindrical shape or rotary drum shape photoreceptor substrate is included in and applies impregnated substrate in the bath.By the bath that in the solvent solution of film forming polymer, disperses photoconductive pigment particles preparation to be used to prepare photoconductive layer.Yet it is crucial that being chosen in of pigment particles, polymkeric substance and solvent solution reaches in the high-quality light conductance layer.
In this regard, some organic photoconductive pigment particles can not be applied to form high-quality photoelectricity by dip-coating and lead coating.For example, the phthalocyanine color particle tends to sedimentation, and it needs constant stirring to guarantee uniform dispersion.Yet stirring can cause pockets of entrapped air tend, and this air bubble is carried in the final photoconductive coating that deposits on the photoreceptor substrate.Owing to have the zone of bubble therein and wherein do not exist these bubbles of difference of charged photoreceptor discharge between the zone of bubble in final copy, to cause defective.Therefore, for example, final copy during region of discharge develops in display white zone on the bubble demonstration stain when adopting charging zone to develop maybe.
In addition, when in the solvent solution of attempting at film forming polymer during dispersed color, many pigment particles tend to agglomeration.This agglomeration causes uneven photoconductive coating, and it causes other copy defective owing to inhomogeneous discharge and then in final xerox copy.These defectives can be seen with striped and short of electricity lotus point form.The film forming polymer that selection is used for the photoconductive pigment particles of charge generating layer can influence the particle dispersing uniformity unfriendly, coating composition rheology, the residual voltage after wiping and electronic photographic sensitive degree.Some polymkeric substance can cause unsettled pigment particles dispersion, and this dispersion is unsuitable for the dip-coating photoreceptor.Therefore, for example, when the copolymer reaction product of 86wt% vinyl chloride and 14wt% vinyl acetate is used to disperse the photoconductive particle of hydroxy gallium phthalocyanine (OHGaPc) as the VYHH terpolymer from UnionCarbide, obtain unsettled dispersion.In addition, the charge generating layer that comprises this multipolymer has poor light sensation luminosity and obtains high residual voltage after wiping.
In addition, the combination of some polymkeric substance can cause unacceptable coating or electrical property.For example, some polymkeric substance are compatible with each other and can not form wherein in whole final coating the coating of even distribution polymer or particle.Similarly, choice of Solvent influences the quality of dispersion and the easy degree of manufacturing process.For example, be dissolved in the polycarbonate base-material of tetrahydrofuran or toluene, poly-(4,4 '-diphenyl-1,1 '-cyclohexane carbonic ester) cause the non newtonian dispersion.
By this thinking, these problems also are disclosed in people such as Nealey, United States Patent (USP) 6,017,666, people such as Nealey, United States Patent (USP) 5,681,678, people such as Nealey, United States Patent (USP) 5,725,985, people such as Burt, United States Patent (USP) 5,456,998 and people such as Nealey, United States Patent (USP) 5,418,107, the disclosure of these documents is incorporated herein by reference fully at this.Although these patents have proposed the use base-material and solvent is produced the charge generating layer matrix to strengthen photoconductive particle dispersing uniformity etc., still need further improvement.
Therefore, need other method and composition to form the charge generating layer of image-forming component, it shows the dispersion stabilization that strengthens, the charge migration performance of enhancing etc.
Summary of the invention
Disclose a kind of method that forms charge generating layer at this with multiple embodiments, this method has overcome one or more above-mentioned defectives.Described method is included in disperses photoconductive phthalocyanine particle in polymeric matrix in the solution of n-butyl acetate (NBA) and methyl isobutyl ketone (MIBK), described matrix comprises the polymer film forming reaction product of vinyl chloride, vinyl acetate, carboxylated monomer such as maleic acid and acrylic acid hydroxy alkyl ester.Then with the charge generating layer of dispersion paint substrate with the formation electrophotographic imaging member.This dispersion is suitable for use as organic photoconductive coating (OPC) or active matrix coating (AMAT).
A kind of electrophotographic imaging member also is provided, this element comprises substrate, charge generating layer and transmission of electricity layer, charge generating layer is prepared by following mode: disperse photoconductive phthalocyanine particle in the solution of NBA and MIBK in polymeric matrix, described matrix comprises the polymer film forming reaction product of vinyl chloride, vinyl acetate, carboxylated monomer such as maleic acid and acrylic acid hydroxy alkyl ester at least; With dispersion paint substrate, and dry it.
Description of drawings
Fig. 1 is photoinduced discharge curve (PIDC), and this curve representation adopts 60: 40 pigment by weight according to an embodiment of present disclosure: the photoreceptor of polymer ratio preparation.
Fig. 2 is photoinduced discharge curve (PIDC), and this curve representation adopts 35: 65 pigment by weight according to an embodiment of present disclosure: the photoreceptor of polymer ratio preparation.
Fig. 3 is the flow visulization of adopting and do not adopt the OHGaPc/U527/NBA dispersion of MIBK.
Embodiment
Electrophotographic imaging member, promptly photoreceptor is well known in the art.Typically, provide substrate with conductive surface.Then with at least one photoconductive layer paint conductive surface.Can be optionally with electric charge barrier layer paint conductive surface before the applying of photoconductive layer.As needs, bonding coat can adopt between electric charge barrier layer and photoconductive layer.For multi-layer photoreceptor, will give birth on the common paint of the electric binder layer restraining barrier and will transmit electricity the layer on charge generating layer, form.Yet, as needs, can be with charge generating layer paint transmission of electricity layer.
Substrate can be many suitable materials opaque or substantially transparent and that can comprise the mechanical property with requirement.Therefore, substrate can comprise layer non-conductive or conductive material such as inorganic or organic composite.Can adopt for the known various resins of this purpose as non-conducting material, comprise polyester, polycarbonate, polyamide, polyurethane etc., they are rigidity or flexible, as thin net.
The thickness of substrate layer depends on many factors, comprise beam intensity and economic consideration and therefore be used for flexible band this layer can for enough thickness for example, about 125 microns, or less than 50 microns minimum thickness, condition is that final eletrophotography equipment is not had adverse influence.In a flexible band embodiment, when centering on the minor diameter roller as 19 mm dia roller circulation times, for the pliability and the minimum stretch of optimum, the thickness of this layer is about 65 microns-Yue 1 50 microns and preferred about 75 microns-Yue 100 microns.Depend on required rigidity degree, the substrate that is shaped as rotary drum or cylinder can comprise metal, plastics or the metal of any suitable thickness and the combination of plastics.
Depend on required optical clarity of electrophotographic imaging member and pliability degree, conductive layer can be in wide substantially scope variable thickness.Therefore, for flexible photoresponse imaging device, for conductivity, the optimum combination of pliability and transmittance, the thickness of conductive layer can be about 20 angstrom units-Yue 750 angstrom units and 100 angstrom units-Yue 200 angstrom units more preferably from about.The compliant conductive layer for example can be, the conductive metal layer that is formed by any suitable paint-on technique such as evaporating deposition technique on substrate.At substrate is that metals like gold belongs under the situation of rotary drum, its outside surface normally be inherently conduction and do not need to apply independent conductive layer.
After the formation of conductive surface, can apply hole blocking layer to it.Usually, the electronic barrier layer that is used for the positively charged photoreceptor allows the hole to move to conductive layer from the imaging surface of photoreceptor.Can adopt can the adjacent light conductance layer and below conductive layer between form any suitable restraining barrier to the electronic barrier in hole.The restraining barrier be known and, for example be disclosed in United States Patent (USP) 4,291,110,4,338,387,4,268,033 and 4,291,110.United States Patent (USP) 4,338,387,4,286,033 and 4,291,110 disclosure is introduced in full at this.
Can be with non-essential bonding coat paint hole blocking layer.Can adopt any suitable bonding coat well known in the art.Can adopt the about 0.05 micron-bondline thickness of Yue 0.3 micron (3,000 dust) to reach gratifying result.Apply the bonding coat coating compound to the routine techniques of electric charge barrier layer comprise that spraying, dip-coating, roller coat, coiling rod are coated with, intaglio plate coating, Bird(film)applicator coating etc.The drying of deposition coating can be undertaken by any suitable routine techniques such as oven drying, infrared radiation drying, air drying etc.
In charge generating layer, photoconductive phthalocyanine particle is as the organic photoconductive pigment particles.These particles are dispersed in the polymeric matrix.Suitable phthalocyanine particle comprises hydroxy gallium phthalocyanine, does not contain the x metal phthalocyanine, titanyl phthalocyanine, gallium chlorine phthalocyaninate and vanadyl phthalocyanine and their polymorph.For example, any suitable hydroxy gallium phthalocyanine polymorph can be used for the charge generating layer of the photoreceptor of this disclosure.The hydroxy gallium phthalocyanine polymorph extensively is described in the technical patent document.For example, V-type hydroxy gallium phthalocyanine and other polymorph are described in United States Patent (USP) 5,521,306, and the whole disclosure of this patent is hereby incorporated by.Usually, the photoconductive pigment particle size of employing less than the thickness of dry charge generating layer and particle mean size less than about 1 micron.When applying photoconductive coating, adopt and reach gratifying result less than about 0.6 micron average photoconductive particle size by dip-coating.Preferably, average photoconductive particle size is less than about 0.4 micron.Employing reaches optimal result less than about 0.2 micron particle mean size.
Polymeric matrix in the charge generating layer of present disclosure comprises the polymer film forming reaction product of vinyl chloride, vinyl acetate, carboxylated monomer such as maleic acid and acrylic acid hydroxy alkyl ester.These reactants can form the skeleton that quadripolymer and final quadripolymer comprise carbon atom.Can be by reacting condition temperature and time control quadripolymer chain length.For being used for charge generating layer of the present invention, the polymkeric substance of this embodiment can form from the reaction mixture that comprises following material: the about 90wt% vinyl chloride of about 80wt%-, the about 15wt% vinyl acetate of about 3wt%-, the about 20wt% acrylic acid hydroxy alkyl ester of about 6wt%-and carboxylated monomer of about at the most 0.4wt% such as maleic acid are based on the general assembly (TW) of the reactant that is used for polymkeric substance.
For example, the ratio that exists in final polymeric matrix of maleic acid can not influence the quality or the coating quality of dispersion unfriendly for the about 0.4wt% of 0wt%-.
Polymkeric substance can be represented by following general formula:
Wherein
R is the alkyl group that comprises 2-3 carbon atom,
R is the ratio derived from the polymkeric substance of the reaction mixture that comprises the about 90wt% vinyl chloride of about 80wt%-,
S be derived from the ratio of the polymkeric substance of the reaction mixture that comprises the about 15wt% vinyl acetate of about 3wt%-and
T be derived from the ratio that comprises the polymkeric substance of the reaction mixture of 0.4wt% maleic acid at the most and
U is the ratio derived from the polymkeric substance of the reaction mixture that comprises the about 20wt% acrylic acid hydroxy alkyl ester of about 6wt%-, based on the general assembly (TW) of the reactant that is used for polymkeric substance.
The film forming polymer of this embodiment is commercially available and for example comprises, UCARMag 527 resins, its number-average molecular weight is about 35,000, be 81wt% vinyl chloride, the 4wt% vinyl acetate, the polymeric reaction products of 15wt% hydroxy-ethyl acrylate and 0.28wt% maleic acid (available from Union Carbide Co.).When polymkeric substance is that number-average molecular weight can reach gratifying result when being about 35,000 solvent soluble polymkeric substance.Preferably, the number-average molecular weight of these polymkeric substance is about 20, and 000-about 50,000.When molecular weight less than about 20,000 o'clock, may run into poor filming performance and not required dispersing characteristic.
The moieties that is used for the acrylic acid hydroxy alkyl ester reactant of above-mentioned polymkeric substance comprises 2-3 carbon atom and comprises for example ethyl, propyl group etc.Acrylic acid hydroxy alkyl ester reactant ratio less than about 6% can influence the quality of dispersion unfriendly.After being formed into membrane polymer, polymkeric substance preferably includes the carbonyl hydroxyl multipolymer of hydroxy radical content for the about 5wt% of about 1wt%-, based on the general assembly (TW) of polymkeric substance.Also can be used in combination above mixture of polymers with any.
Can be used for disperseing the dicyandiamide solution of photoconductive pigment particles and film forming polymer to form by n-butyl acetate (NBA) and methyl isobutyl ketone (MIBK).When dispersed color particle and polymkeric substance, dicyandiamide solution preferably is made up of about 95%NBA of about 40%-and the about 60%MIBK of about 5%-, and calculating by the weight of solvent (is NBA and MIBK; The weight that does not comprise pigment and polymkeric substance).Most preferably, dicyandiamide solution is made up of about 65wt%NBA and about 35wt%MIBK.This ratio provides high coating quality, more uniform dispersion and more uniform flowing around barrier.In addition, this dicyandiamide solution allows to apply and dry charge generating layer under environmental baseline then.
Can show by the flow visulization test by improvement as the flow uniformity of the introducing of the MIBK of second solvent.In this type of test, make the too small gap of this stream of dispersion, as 0.5 mil, barrier is arranged in stream wherein.Being fixed together by two stainless steel gasket bars with two microslides and given thickness, to form the gap mobile to limit.Flow pattern after barrier can be one of standard of dust dispersion quality.The ideal of dip-coating disperses not have striped after barrier.Fig. 3 shows an example, and how the introducing that MIBK is described improves the dust dispersion quality with regard to flow uniformity around the barrier, and wherein 35%MIBK greatly reduces striped behind the barrier.
Any suitable technique all can be used for the dispersed color particle and film forming polymer is gone into suitable solvent.Typical dispersion technology for example comprises, ball milling, roller mill, milling in vertical grinding mill or horizontal three-dimensional bowl mill, sand milling and adopt those of the medium of milling.Be not revealed as crucial by the solids content of the potpourri of being milled and can be selected from wide concentration range.
On the substrate that any suitable technique can be used for the coating paint will be applied.Typical paint-on technique comprises dip-coating, roller coat, spraying, rotary atomizer etc.Paint-on technique uses wide solid concentration scope.
When comprising the about 80wt% photoconduction of about 40wt%-phthalocyanine particle, the photoconductive coating of drying reaches gratifying result, based on the general assembly (TW) of dry charge generating layer.When pigment concentration during less than about 40wt%, lost particle contacts particle, causes deterioration.When charge generating layer comprises about 60wt% photoconduction particle and about 0.2 micron average pigment particle size, reach optimal performance, based on the general assembly (TW) of dry charge generating layer.Because the photoconductor characteristic is by every square centimeter pigment relative populations and particle size influences applying, if therefore adopt the dry photoconductive dope layer of identical pigment particle size thicker, pigment content can be lower.On the contrary, under the thin situation of the photoconductive layer of drying, need higher pigment content.
Multi-layer photoreceptor for comprising charge generating layer and transmission of electricity layer adopts about 0.1 micron-Yue 10 microns dry photoconductive layer paint thickness can reach gratifying result.Preferably, photoconductive layer thickness is about 0.2 micron-Yue 1 micron.Adopting thickness is that about 0.2 micron-Yue 0.7 micron generation layer reaches gratifying result.Yet these thickness also depend on pigment content and size-grade distribution.Therefore, higher pigment loads the photoconductive coating that allows use thinner.Can be chosen in these scopes thickness in addition, condition is to reach purpose of the present invention.
Active transmission of electricity layer can be included in any suitable activating compounds that is used as adjuvant in the electric inert polymer material, and it is electroactive making these materials.Any suitable arylamine hole-transfer thing molecule can be used for image-forming component of the present invention.
These compounds can be joined in the following polymeric material, that is, this material can not support photohole from injection that produces material and the transmission that can not allow these holes to pass through.This polymeric material that can transform electric inertia becomes can support photohole from injection that produces material and the material that can allow these holes by the transmission of active layer, so that the surface charge on the active layer is discharged.The preferred especially transfer layer that is used for one of two electric operation layers of Heterolamellar photovoltaic conductor of the present invention comprises wherein aromatic amine compatible polymers film-forming resin of at least a charge migration aromatic amine compound of the about 75wt% of about 25wt%-and the about 25wt% of about 75wt%-.
Any suitable inert plastic base-material that is dissolved in methylene chloride, tetrahydrofuran, toluene etc. and composition thereof can be used for method of the present invention.
Any suitable and conventional technology can be used for mixing and applies transmission of electricity coating potpourri thereafter to applying or uncoated substrate.
Usually, the thickness of hole transport layer is about 50 microns of about 10-, but also can use the thickness beyond this scope.Hole transport layer should be an insulator to following degree: in the presence of the illumination not be enough to prevent electrostatic latent image from forming thereon and the speed that keeps under the conduction static charge of on hole transport layer, placing.Usually, hole transport layer preferably remains about 2 to the ratio of the thickness of charge generating layer: 1-200: 1 and in some cases greatly to 400: 1.
Preferred electric inert plastic material is that molecular weight is about 20, and 000-is about 150,000, more preferably from about 50, and the polycarbonate resin of 000-about 120,000.Be that molecular weight is about 20 as the material of electric inert plastic material most preferably, 000-is about 40,000, with PCZ400 available from MitsubishiChemicals poly-(4,4 '-diphenyl-1,1 '-cyclohexane carbonic ester; Molecular weight is about 40, and 000-is about 45,000, with poly-(4,4 '-isopropylidene-diphenylene carbonic ester) of Lexan 141 available from General Electric Company; Molecular weight is about 50, and 000-is about 120,000, is about 20 with Makrolon available from the polycarbonate resin of Farbenfabricken Bayer A.G. and molecular weight, and 000-about 50,000 is with the polycarbonate resin of Merlon available from Mobay Chemical Company.Because the suitable dissolving of all components and because its low boiling, methylene chloride and tetrahydrofuran solvent are two kinds of required components of transmission of electricity coating potpourri.
Optionally, protective seam also can be used for improving wearing quality.Can wherein make the web frame photoreceptor with the side of the relative photoreceptor of back coating paint of preventing curling so that flatness and/or wearing quality to be provided in some cases.These protective seams and the anti-back coating that curls are well known in the art.Protective seam is that continuous and common thickness is less than about 10 microns.The thickness of anti-curl back layer should be enough to total power of the layer on the opposite side of substrate slice basic unit in a basic balance.The example of anti-curl back layer is described in US-A 4,654,284, and the whole disclosure of this patent is hereby incorporated by.For the about 160 microns thickness of the about 70-of flexible photoreceptor is gratifying scope.
Embodiment 1
By in 100%NBA, being dissolved into the membrane polymer composition and adding hydroxy gallium phthalocyanine pigment prepared dispersion then.Polymkeric substance is by polymer weight 81wt% vinyl chloride, the 4wt% vinyl acetate, and the polymeric reaction products of 0.28wt% maleic acid and 15wt% hydroxy-ethyl acrylate and number-average molecular weight are about 35,000 (UCARMag 527, available from Union CarbideCo.).Pigment concentration in the dispersion is 60wt%, based on total solid weight (pigment and polymkeric substance).In vertical ball mill, adopt the 1mm diameter glass beads to mill 0.5-10 hour dispersion.The dispersion filtration is used for applying to 4-5% to remove bead and to regulate solids content.The potpourri of use NBA and MIBK is regulated and is made that the final solvent strength of dispersion is 65%NBA and 35%MIBK.(BrookhavenInstruments, Inc.), the mean effective diameter of the pigment particles of milling is about 0.15-0.3 μ m by BI-90 plus particle size analyzer.Check the dust dispersion quality of coating compound by the flow pattern homogeneity of measuring it.Then, the long aluminium rotary drum of cylindrical shape 40mm diameter and 310mm coating base coat, this undercoat are that 4 μ m are thick and comprise 58wt% titania by drying bottom coating weight, 4wt% silicon dioxide, and 4wt%Varcum.Apply living electrodispersion body by the aluminium rotary drum being immersed give birth to the electrodispersion body and extract it along the approach that is parallel to the rotary drum axle out with the speed of 200mm/min in vertical direction.The living electrocoating paint that applies was approximately the layer of 0.3 μ m in dry 10 minutes with formation thickness under environment.Then this charge generating layer is adopted by PCZ400/N N '-diphenyl-N, two (the 3-aminomethyl phenyls)-1 of N-, 1 '-biphenyl-4, the charge migration potpourri dip-coating of 4 '-diamines/THF/ monochloro benzene.The charge migration coating that applies is descended dry 40 minutes to form the layer that thickness is 24 μ m by the pressure air-oven at 135 ℃.In following table, sum up the performance of the living electrodispersion body be used to prepare photoreceptor:
Pigment/polymer ratio Wt.% The % solid Viscosity (cps) Granularity (μ m) Power law fit Yield point
60/40 4.5 2.2 0.15-0.3 ＞0.98 0
By doing slope acquisition " power law " statement of viscosity to the line of shear rate log-log figure and measurement acquisition.Approximate 1 numerical value indication Newton type fluid does not promptly show viscosity change with the shearing that increases.Viscosity number adopts centipoise unit.Statement " yield point " is defined as the resistance to flow till applying some shear force.Approximate 0 numerical value does not have yield point and is required for the dip-coating purpose.This yield point numerical value is illustrated in and does not observe yield point in this dispersion.
Reference examples 1
Use the process preparation contrast photoreceptor of embodiment 1, difference is that film forming polymer is by polymer weight 86wt% vinyl chloride, 13wt% vinyl acetate, polymeric reaction products with the 1wt% maleic acid, with number-average molecular weight be about 27,000 (VMCH is available from UnionCarbide Co.).
Embodiment 2
Use the process of embodiment 1 to prepare photoreceptor, difference is that the pigment concentration in the dispersion is 35wt%, based on total solid weight (pigment and polymkeric substance).
Reference examples 2
Use the process preparation contrast photoreceptor of embodiment 2, difference is that film forming polymer is by polymer weight 86wt% vinyl chloride, and the polymeric reaction products of 13wt% vinyl acetate and 1wt% maleic acid and number-average molecular weight are about 27,000 (VMCH is available from Union CarbideCo.).
The result
Photoreceptor and its contrast photoreceptor (reference examples 1) to preparation in embodiment 1 adopt scan round device equipment to carry out electrical testing to obtain 100 charging-erase cycles, immediately carry out other 100 circulations, order by 2 charging-erase cycles and 1 charging-exposure-erase cycles is carried out, wherein light intensity increases to produce photoinduced discharge curve (PIDC) with circulation cumulatively, measures photographic sensitivity from it.Scanner assembling single line corona (5cm is wide) device is to deposit 80nC/cm on the photoreceptor surface 2Electric charge.In negative charge mode, test photoreceptor.A series of neutral density filters increase the exposure light intensity cumulatively and exposure wavelength is controlled at 780 ± 5nm by bandpass filter by regulating.Exposure light source is 1,000 watt of xenon arc lamp white light source.At 80nC/cm 2Single charging cycle (the not wiping) dark discharge of measuring photoreceptor by monitoring surface potential 7 seconds afterwards.Photographic sensitivity (dV/dx) is defined as about 70% (about 7 ergs of about 0-/cm of initial voltage from initial discharge rate calculations under low exposure intensity 2Exposure).Giving birth to electrical efficiency is that 1/2 place determines critical voltage, V cRotary drum was rotated under the speed of 40rpm with the superficial velocity of generation 62.8mm/sec or 1.5 seconds cycling time.Xerox simulation is carried out under environmental baseline (30% relative humidity and 25 ℃) in the darkroom of environment control.For measuring photoinduced dark discharge speed, photoreceptor is in the dark placed 24hrs, apply single charging cycle then and in the dark measure the voltage attenuation that obtains.The photoreceptor that the dark discharge electric current is placed for the dark place of example I and reference examples I is carved identical at this moment.Subsequently sample is exposed to 300 negativity charging-erase cycles and allows in the dark to decay in last charging cycle.Calculate photoinduced dark discharge speed from the difference between two dark decay voltage speed.After 300 negativity charging-erase cycles, the photoreceptor of example I shows the less dark decay speed of about 2V/s, shows the improved transmission capacity that is reached by charge generating layer among the present invention.The results are summarized in following table:
Equipment Initial voltage V o(V) Photographic sensitivity (Vcm 2/erg) Critical voltage V c(V) Residual voltage V r(V) The photoinduction dark discharge
Embodiment 1 711 441 105 54 7.8V/s
Reference examples 1 712 436 114 55 9.7V/s
Two photoreceptors have identical thickness and are charged to identical initial voltage, discharge into then at 1V with interior identical residual voltage.The photoreceptor of embodiment 1 shows higher slightly photographic sensitivity, and indication is in charge generating layer and at the charge migration of enhancing at the interface of charge generating layer and other layer.Have significant difference aspect critical voltage, it is the tolerance from the precipitous degree that departs from of the linear segment of PIDC.In idealized system, PIDC is linear in the rest potential point by the charge mobility limit dictates that exists in the system.In multi-layer photoreceptor equipment, the charge migration in each layer and the electric charge at their interfaces to inject both be crucial and fit over reach rest potential before the transition region of curve.The lower V of the photoreceptor of embodiment 1 cThe excellent properties of showing charge generating layer prepared in accordance with the present invention.This shows that in Fig. 1 wherein two photoreceptors have identical initial slope, but the photoreceptor of embodiment 1 shows precipitous at the maximum curvature place of PIDC.The photoreceptor of embodiment 2 and reference examples 2 shows similar result.Fig. 2 is illustrated in the identical precipitous of PIDC maximum curvature place.

Claims (3)

1. one kind prepares the method that is applicable to the dispersion of charge generating layer paint substrate, and this method comprises:
Dissolving comprises that the polymer film forming product of vinyl chloride, vinyl acetate, carboxylated monomer and acrylic acid hydroxy alkyl ester is to form solution in n-butyl acetate;
Disperse photoconductive phthalocyanine particle in this solution, the particle mean size of described photoconductive phthalocyanine particle is less than 1 micron, and makes dry photoconductive coating comprise 40wt%-80wt% photoconduction phthalocyanine particle based on the general assembly (TW) meter of dry charge generating layer; With
Add methyl isobutyl ketone and have the final dispersion of following solvents system with formation, this dicyandiamide solution comprises 40wt%-95wt% n-butyl acetate and 5wt%-60wt% methyl isobutyl ketone by weight of solvent.
2. dispersion comprises:
Polymeric matrix, this matrix comprise the polymer film forming product of vinyl chloride, vinyl acetate, maleic acid and acrylic acid hydroxy alkyl ester;
Photoconduction phthalocyanine particle, the particle mean size of described photoconductive phthalocyanine particle be less than 1 micron, and dry photoconductive coating comprises 40wt%-80wt% photoconduction phthalocyanine particle based on the general assembly (TW) meter of dry charge generating layer; With
Dicyandiamide solution, it comprises 60-75wt% n-butyl acetate and 25-40wt% methyl isobutyl ketone by weight of solvent.
3. image-forming component comprises:
Substrate;
Charge generating layer; With
The transmission of electricity layer;
Wherein said charge generating layer is prepared by following mode:
In the solution of the dicyandiamide solution of forming by 65wt% n-butyl acetate and 35wt% methyl isobutyl ketone, in polymeric matrix, disperse photoconductive phthalocyanine particle, the particle mean size of described photoconductive phthalocyanine particle is less than 1 micron, and make dry photoconductive coating comprise 40wt%-80wt% photoconduction phthalocyanine particle based on the general assembly (TW) meter of dry charge generating layer, described matrix comprises the polymer film forming reaction product of vinyl chloride, vinyl acetate, maleic acid and acrylic acid hydroxy alkyl ester;
With the described substrate of described dispersion paint; With
Dry described dispersion.
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US7410743B2 (en) * 2005-05-27 2008-08-12 Xerox Corporation Imaging systems and method that form a layer on an imaging member
US7799501B2 (en) * 2007-05-31 2010-09-21 Xerox Corporation Photoreceptors
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